Alkenoxy amino diphenylamines



Patented Sept. 7, 1948 ALKENOXY AMINO DIPHENYLAMINES Robert P. Parker, Somerville, and John J. Denton, Bound Brook, N. J., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application July 3, 1944,

i Serial No. 543,434

8 Claims. (01. 260-571) 1 'This invention relates to 4-alkenyloxy-4-aminodiphenylamines.

Y The compounds of the present invention may be represented by the following formula:

in which Alk is an alkenyl radical. Salts of the compounds with strong acids are also included.

The compounds of the present invention are useful in the production of 2.20 dyestuffs. When diazotized and coupled, particularly with icecolor coupling companents, azo dyestuffs are obtained which exhibit superior fastness properties such as fastness to light, heat and washing and the colors retaintheir brightness well.

The compounds of the present invention may be prepared by reacting 4-hydroxy-4-nitrodiphenylamine or its 2-sulfonic acid derivatives with an alkenyl ester such as an alkenyl chloride, bromide or iodide. The reaction with the alkenyl halides is preferably carried out in the presence of an acid binding'agent. It is, also, preferred to effect reaction in solution for which purpose aqueous alcohols are preferred. The nature of the solvents is not critical and it is an advantage that a wide range of organic solvents are useful. Typical further examples are acetone and dioxane. Suitableacid binding agents are numerous; I

such as the alkali metal and alkaline earth metal carbonates, alkaline earth metal oxides, the alkali and alkaline earth metal hydroxides and the alkali-metal alkoxides. The choice of the alkenyl halide is not critical, but as the bromides and iodides do not present material advantages over the chlorides, the latter are preferred by reason of their cheapness and commercial availability.

When the initial nitro compound is prepared from 4-hydroxy 4 nitrodiphenylamine-Z-sulfonic acid, and it is desired to remove the sulfonic acid group, this may be effected before or after reduction of the nitro group.

It is an advantage of the present invention that the reductionof the nitro group to the amino group may be readily accomplished by either alkaline or acidic reducing agents. The pH of the reaction medium will determine whether the amino compounds are obtained in the form of the free base or as their salts. The principal value of thecompounds is in the production of azo dyes and for this purpose it is immaterial whether the compound is in the form of the free base or a'salt.

Typical alkenyl groups which may be present in the compounds of thepresent invention are the following; allyl, Z-methylallyl (methallyl) 2- chloroallyl, Z-cyanoallyl, crotyl, 3,3-dimethylallyl, and 2-fluoroallyl. The invention will be described in conjunction with the following examples which illustrate the production of representative compounds of the present invention and their use in the production of some azo dyestuffs. All parts.

are by weight unless otherwise noted.

Example 1 4-allyloxy-i-aminodiphenylamine hydrochloride A mixture of 2? parts of 4'-allyloxy-4-nitrodiphenylamine, parts 37% sodium sulfhyd-rate, and 79 parts of alcohol is stirred continually in a reaction vessel and heated under reflux for four hours. It is cooled and a copious precipitate of 4'-allyloxy-4-aminodiphenylamine forms when 100 parts of water is added slowly. Thi slurry is further diluted with 200 parts of water, and the solid is collected on a filter. After being washed free of mother liquor, the amine is isolated in the form of its hydrochloride by being dissolvedln hot, dilute hydrochloric acid, the solution filtered, chilled, and the 4'-allyloxy-4-aminodipheny1- amine hydrochloride salted out with sodium chloride.

Example 2 Eleven and one-tenth parts of 4-allyloxy-4- aminodipheny-lamine hydrochloride as obtained in Example 1 are slurried in 200 parts of water containing 48 parts of 17% hydrochloric acid. The slurry is kept at 15 C. while being diazotized slowly by dropwise addition of a solution of 3 parts of sodium nitrite in 44 parts of water. The resulting slurry is diluted with approximately parts of water, heated to 50 0., treated with decolorizing charcoal, and filtered. The clear, red-orange solution resulting is chilled in an ice bath, and the diazonium chloride of 4'-allyloxy- 4-amino diphenylamine is precipitated as an orange solid through addition of sodium chloride. It is filtered off and is dried at low temperature. It is readily soluble in water.

Example 3 A dry mixture is made from 3.3 parts of the di' azonium chloride as prepared in Example 2 from 4'-allyloxy-4-amino-diphenylamine, 2 parts of 3 magnesium sulfate dihydrate, and 1 part of anhydrous sodium sulfate. I Two parts of this dry mixture are dissolved in parts of water and the solution is treated with '73 parts of suitable carbohydrate thickener. This thickened printing paste is printed from an engraved steel roll on cotton piece goods that have been previously impregnated with the anilide of 2-hydroxy-3-naphthoic acid grounding liquor. The printed stripe is dried at C., is cleared in a hot dilute soda ash bath, is treated in /2% soap solution at 60 C., is rinsed and dried. I

The pattern is printed a strong blue of greenish shade which shows superior fastness properties.

Example 4 4-methallyloxyA-nitrodiphenylaminc To a solution of 9.5 parts sodium methylate and 3&5 parts 4'-hydroxy-4-nitrodiphenylaminein 197 parts of absolute alcohol is added 14.9 parts methallylchlori-de. The reaction mixture .is heated under reflux for six hours. After heating it is cooled, and 150 parts of water is 29.7 parts of .4'-methallyloxy-4-nitrodiphenylamine is suspended in parts of 37% sodium sulfhydrate solution and 59 parts of ethyl alco- 1101 and the Whole refluxed with continuous agitation for a number of hours until reaction is complete. After the reaction mixture is cooled, the addition of a few parts of water causes the amine to solidify and results in a smooth slurry. This slurry is diluted with 200 parts of water, and the solid 4-methallyloxy-4-aminodiphenylamine is collected on a filter and washed thoroughly with water containing sodium hydrosulfite. The amine is obtained in the form of its hydrochloride by dissolving in warm, very dilute hydrochloric acid, treating with decolorizing charcoal, filtering, cooling in an ice bath, and salting out with sodium chloride. The crystalline 4-methallyloxy 4 aminodiphenylamine hydrochloride which formsis collected on a filter and dried.

Example 6 A.mixture of 11.6 parts of 4-methallyloxy-4- aminodiphenylamine hydrochloride (as obtained in Example 5), 150 parts of water, and 48 parts of 17% hydrochloric acid is stirred and cooled to 15 C. and kept at'that temperature while being diazotized with a solution of approximately 3.3 parts sodium nitrite in 49 parts of water. After diazotization is complete, the mixture is diluted with about 300 partsof water, warmed and stirred in an alkaline collected on a filter and dried. It is readily soluble in water. 7

Example 7 sulfates When 2.0 parts of this mixture are converted to a printing paste and printed according to the procedure as described in Example 3 on cotton fabric previously impregnated with the aniline of 2-hydroxy-3-naphthoic acid and finished by the procedure described, a heavy blue of strong reddish shade and. good fastness properties is obtained.

Example 8 10.2 parts of the sulfate salt of 4'-(al1yloxy)- e-aminoiphenylamine are slurried in a mixture of parts of water and 8.0 parts of 20% sulfuric acid. After stirring vfor V2 hour the temperature is adjusted to 15 C. and'the slurry is diazotized by slow addition of 3.2 parts of sodium nitrite dissolved in 40 parts of water. The resulting solution is clarified and the chilled filtrate is treated dropwise with 10 parts sulfuric acid'(1.84) and then 10 parts of anhydrous sodium sulfate are strewn in portionwise.

The orange, flaky precipitate of thediazonium acid sulfate of 4-(allyloxy)-4-aminodiphenylamine is collected on the filter and is dried at low temperature.

Example 9 'When 0.2 part of the dry diazonium acid "sulfate obtained as described in Example 8, slurried in 2.5 parts methanol, is treated with a slurry of 2.0 parts of beta-naphtho'l in 2.5 parts of methanol and 3.0 parts of pyridine, a thick blue-black paste is obtained. This is heated'for 10 minutes on a steam bath, is diluted With 200 parts of water and 20% sodium hydroxide is added until the resulting slurry is well alkaline to phenolphthalein paper. The dyestuff is flocculated by digestion on the steam :bath, is filtered off, washed well with hot water, then with dilute hydrochloric acid, finally by hot water- After drying, a deep blue pigment is obtained. insoluble in water.

Example 10 4.0 parts of the dry diazonium acid 'sulfateof 4'- (allyloxy) -4-aminodiphenylamine .as obtained in Example '8 are intimately mixed with 2.2 parts magnesium sulfate dihydrate and 1.1 parts of anhydrous sodium sulfate. v

This product is used to'produce developed dyeings on cotton fabric by the following procedure:

Cotton'fab'ric is treated in alkaline groundin baths comprising: 5 parts of ice color coupling component, .5 :part of methanol, 20 partsof 20% sodium hydroxide solution and 470 parts of water. The treated cloth is passed between squeeze rolls and is immediately dried'at 65 C.

5.0 parts of the fabric so treated is entered into dye baths containing 0.5 part of the above dry blended mixture dissolved in 250 parts of water and while the fabric is efliciently agitated 5 parts of 20% sodium acetate solution isrun in.

When full color development is attained, the fabric is rinsed, is cleared at 70 C. in an alkaline solution (3% soda ash and 2% sodium hydroxide) for2 minutes, treated at 70 C. in a /2% soap solution, rinsed in fresh Water and dried.

The colors obtained with various ice color coupling components are as follows:

Ice Color Coupling Component Color 2-Hydroxy-3-naphthoic acid anilide green-blue. 2-Hydroxy-3-naphthoic acid-(T-methylanil de).. blue. 2-Hydroxy-3-naphthoic ac1d-(2-ethoxyan1llde) navy blue. Bis-(acetoacetic)-o-tolidide yellow-brown. 2-Hydroxy-3-naphthoic acid-(4-el1l0r0ani]1de).- blue. 2-Hydroxy-3-naphthoic acid-(3-nitranilide) green-blue. 2-Hydroxy-3-anthracenc carboxylic acid-(5% dark green.

methylanilide). 2-Hydroxy 3-carbazole carboxylic acid-(2-metl1- chocolate.

ylanilide).

Example 11 The dry, blended mixture of the diazonium chloride of 4-(methallyloxy) -4-aminodiphenylamine as made in Example '7 is use-d to produce developed dyeings on cotton fabric previously impregnated with ice color coupling components by the procedure as described in Example 10. The colors produced are listed below:

Ice Color Coupling Component Color 2-Hydroxy-3-naphthoic acid anilide navy blue. Bis-(aceto-acetic)-benzidide darl: tan. 2-Hydroxy-3-naphthoic acid-(2-methoxyan1lide) bluish black. z-Hyldroxy-ii-naphthoic acid-(2-methyl-4-chloroanreddish blue.

ili e Example 12 4-(2"-cl1loroallyloxy)-4-nitrodiphenylamine Exampl 13 4-(2"-chloroallyloxy)-4-aminodiphenylamine hydrochloride OH2=CCH2O NHLHCI 222 parts of iron powder, 240 parts of water, one part of glacial acetic acid and a pinch of gardinol" are charged in the reaction vessel and the temperature is raised to 75 C. At this temperature 12.2 parts of 4-(2"-chloroallyloxy) -4- nitrodiphenylamine are added and the mixture is warmed in a water bath 'at 99 C. for five hours. After cooling, the mixture is filtered and the iron sludge is extracted with parts of acetone. The acetone solution is clarified by filtration with charcoal. The clear acetone solution is cooled and when water is added the free base precipitates out asfan oil. This is extracted with ether. and the dihydrochloride of 4-(2"-chloroallyloxy) -4-amiriodiphenylamine is precipitated from this ether solution by the addition of dry hydrogen chloride. When purified by crystallization from dilute hydrochloric acid, the monohydrorlililosr iigi salt is produced which melts at Example 14 3.5 parts of 4'-(2"-chloroallyloxy)-4-aminodiphenylamine hydrochloride are dissolved in a solution of 12 parts of 1'7 hydrochloric acid in 35 parts of water, and the resulting solution is quickly iced to 15 C. A solution of 0.83 part of sodium nitrite in 12 parts of water is added slowly to this solution, and the whole is stirred until the diazotization is complete. The solution is clarified by filtration at 40 C. with diatomaceous earth. The filtrate is cooled and sodium chloride is added. The dlazonium chloride of 4- (2' -chloroallyloxy) -4-aminodiphenylamine precipitates as an oily solid which after separation and drying becomes friable. It may be rapidly dried and solidified by intimately mixing it with an equivalent weight of a mixture of magnesium sulfate-sodium sulfate (two parts magnesium sulfate dihydrate to one part anhydrous sodium sulfate). The resulting blended product is readily soluble in water.

Example 15 One part of the blended diazonium chloride as prepared in Example 14 is dissolved in 300 parts of water and then 5.0 parts of cotton piece goods previously impregnated in an alkaline grounding bath of the ortho-phenetidide of 2- hydroxy-3-naphthoic acid are entered to the dye bath and are well stirred for 10 minutes. The goods are removed, rinsed in fresh water, cleared in boiling dilute soda ash bath, treated in /s% soap solution at 65 0., rinsed in fresh water and dried.

The cloth is evenly dyed a heavy shade of blue.

When instead of the ortho-phenetidide of 2- hydroxy-3-naphthoic acid and anilide is employed in the above dyeing operation, the cloth is dyed a strong blue of redder shade.

We claim:

1. Chemical compounds represented by the formula Alk-O- NH:

in which Alk is a radical selected from the group consisting of allyl, methallyl and beta-chloroallyl radicals.

2. The chemical compound represented by the formula:

CHFCH-CHl-O- NH:

enema 7 3. The chemical: compoundrepresented: by the 8.A salt of a compound of claim 4.

fermwl'a;

e I I 7 ROBERT P. PARKER. CH==CCHr-O N131.- JOHN- J. BENTON.

REFERENCES CITED The following references are of record in the 4. The chenucal compoundrepresented by the fil f this patent;

farm-ma: e r

, 10 UNITED STATES PATENTS Q- N112 Number Name Date Ci 2,278,559 Paul Apr. '7, 1942 NH 2,342,136 Gibbs Feb. 22, 1944 5 A salt of a compound of claim 1. 15 OTHER REFERENCES Arsauiof a compound of 61mm Sidgewicks, Organic Chemistry of Nitrogen? 7. A salt of a compound of claim 3. (1937) (pages 5 g 

